Study of an EE mechanism using double potential step techniques

Manuela Lo pez-Tenes, Marien M. Moreno, Carmen Serna, Angela Molina *

Departamento de Qu mica F sica, Facultad de Qu mica, Universidad de Murcia, Espinardo, ESP-30100 Murcia, Spain
Received 1 March 2002; received in revised form 14 March 2002; accepted 22 April 2002
Abstract
An analytical solution corresponding to the double potential step problem for a reversible EE mechanism is presented. This
solution is applicable to any double pulse technique without restrictions on the duration of the first and second potential steps and is
valid when several species are initially present in the solution. The influence of the duration of the two pulses on the characteristic of
the current /potential curves on differential and reverse double pulse techniques in static and dynamic electrodes is also discussed.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: EE mechanism; Voltammetry; Polarography; Double potential step techniques
1. Introduction
Double pulse techniques in their many forms (differ-
ential normal pulse (DNP), differential pulse (DP),
reverse pulse (RP)) are very useful electroanalytical
tools. So, for example, differential normal pulse has
proved to be an excellent and versatile technique for
trace analysis, since in comparison with other voltam-
metric methods, the potential time sequence can be
chosen to minimise the contribution of capacitative
effects in the measured current [1]. In relation to the
reverse pulse, its principal advantage is to characterise
the product of an electrode reaction, especially with
respect to stability [2].
The study of multistep electrode processes has re-
ceived great attention in the literature, with the two step
(EE mechanism) being the most analysed [3/8]. How-
ever, whereas analytical solutions have been deduced for
an EE mechanism in dc or normal pulse techniques,
there is an evident lack, not to say absence, of analytical
solutions for an EE mechanism when more than one
potential step is applied (multipulse potential techni-
ques). This is because the theoretical treatment of this
last problem is much more complex. In fact, only
numerical solutions have been presented for EE me-
chanisms with multipulse potential techniques [9,10]. In
consequence, a large part of the papers on systems with
multiple charge transfer reactions in multistep potential
techniques offer no more than a qualitative study [11/
15].
In response to this situation, this paper aims to derive
the rigorous analytical solution for a reversible EE
process in any double potential step experiment in such
a way that the two potentials E
I
and E
II
can be applied
without restrictions on the intervals of times, t
1
and t
2
,
respectively. This solution is applicable to electrodes
whose areas increase with an arbitrary power of time z,
with z/0 for a static electrode and z/2/3 for a DME,
and can, therefore, be used in double potential step
chronoamperometry, DNP, DP, and RP voltammetries
and polarographies, whose analytical expressions have
not yet been established.
These expressions are applicable for any value of the
difference of the formal potential of both steps, and also
when all species participating in the electrode process
are initially present in the solution. They can, therefore,
be used for quantitative study of a reversible EE
mechanism and can also be taken as a benchmark for
more complex types of behaviour of this process, for
example: the presence of adsorption or amalgamation,
the consideration of no reversibility of any electroche-
mical step, high values of the rate constants of the
electron exchange reaction in solution, etc.
* Corresponding author. Tel.: /34-968-367-524; fax: /34-68-364-
148
E-mail address: amolina@um.es (A. Molina).
Journal of Electroanalytical Chemistry 528 (2002) 159/169
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0022-0728/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 0 7 2 8 ( 0 2 ) 0 0 9 0 4 - X
2. Theory
We will consider a two-step reversible charge transfer
process (EE mechanism), according to the following
scheme
O
1
n
1
e

?O
2
E
0?
1
O
2
n
2
e

?O
3
E
0?
2
(i)
where E
j
0?
and n
j
(j /1, 2) are respectively the formal
potential and the number of electrons of each step.
In the particular case in which D
1
/D
2
/D
3
the
reaction
n
2
O
1
n
1
O
3
X
k
1
k
2
(n
1
n
2
)O
2
(ii)
cannot be detected with any electroanalytical technique
for any values of k
1
and k
2
[16/18].
We have considered a planar electrode whose area
A(t) increases with an arbitrary power of time z, i.e.
A(t)/A
0
t
z
[19] to which two consecutive potential steps
are applied. When a first potential step E/E
I
is applied
during t with 0/t /t
1
, the expression obtained for the
current for a reversible EE mechanism is the following
(see Appendix A):
I
I

FA(t)

D
1
(2z 1)
_

pt
p fX
I
c(n
2
g
31
c
3
n
1
c
1
)g (1)
X
I

(n
2
g
31
n
1
J
I
1
J
I
2
)
1 g
23
J
I
2
g
13
J
I
1
J
I
2
(2)
with
J
I
1
exp
_
n
1
F
RT
(E
I
E
0?
1
)
_
J
I
2
exp
_
n
2
F
RT
(E
I
E
0?
2
)
_
(3)
cg
13
c
1
g
23
c
2
c
3
(4)
If at time t
1
the potential is stepped from E
I
to E
II
,
which is applied during t
2
, with 0/t
2
/t
2
and t/t
1
/
t
2
, the solution of this problem is more complex than
that corresponding to the application of the first
potential pulse E
I
[20]. We present the solution in
Appendix A, with I
II
being the current observed
I
II
I
I
FA(t)c

D
1
pt
2

h
z
(b)fX
II
X
I
g (5)
where
X
II

(n
2
g
31
n
1
J
II
1
J
II
2
)
1 g
23
J
II
2
g
13
J
II
1
J
II
2
(6)
with
J
II
1
exp
_
n
1
F
RT
(E
II
E
0?
1
)
_
J
II
2
exp
_
n
2
F
RT
(E
II
E
0?
2
)
_
(7)
and X
I
given by Eq. (2).
I
II
has been deduced by supposing that all species O
1
,
O
2
and O
3
can be initially present in the solution and
fulfil the following, interesting relation
I
II
I
II
(c
1
)I
II
(c
2
)I
II
(c
3
) (8)
with I
II
(c
i

) being the current obtained when two

consecutive potential steps are applied and only one
species O
i
(i /1, 2, 3) is initially present in the solution.
Equation (8) is also fulfilled for the current correspond-
ing to a single pulse I
I
(Eq. (1)) [20].
3. Results and discussion
Equation (5), which corresponds to the rigorous
solution for a reversible EE mechanism in a double
potential step problem, will be applied to different
electrochemical techniques. These techniques are called
voltammetries, in a static electrode, or polarographies if
the electrode used is the DME [21]. These cases
correspond to values of z equal to 0 and 2/3, respec-
tively, in all equations of this paper. In particular,
double pulse techniques combine the faradaic currents
at two different potential steps applied without the
equilibrium being re-established and include differential
normal pulse (DNP), differential pulse (DP) and reverse
pulse (RP) techniques. The solutions corresponding to
the techniques using single pulse (normal pulse voltam-
metry (NPV) and normal pulse polarography (NPP))
are also deduced as particular cases of those obtained in
this paper.
3.1. Double pulse techniques with potential steps of
constant amplitude: differential normal pulse voltammetry
(DNPV) and polarography (DNPP)
In these techniques the difference DE/E
II
/E
I
is kept
constant and the currents corresponding to both poten-
tial steps I
II
and I
I
are measured at times t
2
and t
1
,
respectively. The DNP current I
II
/I
I
is recorded versus
E
I
with the pulse amplitude, DE, being scanned either in
the negative (DE /0) or in the positive direction (DE/
0) (see Scheme 1). This current is easily obtained without
restriction on the times of the application of the two
potential steps in DNPV (z/0) or DNPP (z/2/3).
Thus, by subtracting Eqs. (5) and (1) we obtain:
M. Lopez-Tenes et al. / Journal of Electroanalytical Chemistry 528 (2002) 159/169 160
I
DNP

2z1
p
[(t
1
t
2
)
z1=2
(t
1
)
z1=2
]

_
X
I

n
2
g
31
c
3
n
1
c
1

c
_

(t
1
t
2
)
z
h
z
(b)

t
2
p
(X
II
X
I
) (9)
with
I
DNP

I
II
I
I
FA
0
c

D
1
=p
_ (10)
When E
I
, E
II
0/(J
1
I
, J
2
I
, J
1
II
and J
2
II
0/, see Eqs. (2)
and (6)) (upper limit), Eq. (9) becomes
I
upper
DNP


2z1
p
[(t
1
t
2
)
z1=2
(t
1
)
z1=2
]

_
n
1
g
21
c
2
(n
1
n
2
)g
31
c
3

c
_
(11)
and when E
I
, E
II
0// (J
1
I
, J
2
I
, J
1
II
and J
2
II
0/0) (lower
limit) we have
I
lower
DNP


2z1
p
[(t
1
t
2
)
z1=2
(t
1
)
z1=2
]

_
n
2
g
21
c
2
(n
1
n
2
)c
1

c
_
(12)
Note that both the upper and lower limit currents in
the DNP techniques (Eqs. (11) and (12), respectively)
are dependent on the initial concentrations of species
O
1
, O
2
and O
3
and also on the duration of both pulses.
So, for example, if the initial concentration of inter-
mediate O
2
is zero and D
1
/D
2
/D
3
, then from these
limit currents the values of (n
1
/n
2
)c
1

and (n
1
/n
2
)c
3

can
be easily determined.
Eqs. (9) /(12) are valid for any values of t
1
and t
2
. We
will now distinguish the two limit situations t
2
/t
1
and
t
2
/t
1
.
a) When t
2
/t
1
, these equations become those corre-
sponding to differential pulse (DP) techniques, and
from Eq. (9) we obtain:
I
DNP
(t
2
t
1
)I
DP

(t
1
t
2
)
z
h
z
(b)

t
2
p
(X
II
X
I
) (13)
with the upper and lower limiting currents being
zero in these conditions (see Eqs. (11) and (12),
respectively)
I
upper
DP
I
lower
DP
0 (14)
b) When t
2
/t
1
, there are two cases to be distin-
guished: a static electrode (z/0) and a DME (z/
2/3). For z/0 the current corresponding to the
second pulse, I
II
, is negligible in relation to that of
the first pulse I
I
, i. e. I
II
/I
I
. Introducing this
condition in Eq. (10) the current obtained in DNP
techniques will tend towards that obtained in dc
voltammetry
I
DNPV
(t
2
t
1
)
I
I
FA
0
c

D
1
=p
_ (15)
with I
I
given by Eq. (1).
The above explanation cannot be applied to the case of a
DME (z/2/3) for which the growth of the electrode
leads to:
I
DNPP
(t
2
t
1
)
I
I
(E
II
; t
2
)
FA
0
c

D
1
=p
_ (16)
i.e. a current is obtained which is formally identical to
that of the first potential step (Eq. (1)), but which
corresponds to a potential E
II
and to a time t
2
.
Figs. 1 and 2 correspond to a static electrode and a
DME, respectively. These figures show the influence of
the duration of the second potential step, t
2
, on the
normalised DNP curves corresponding to a reversible
EE process by supposing that n
1
/n
2
/1, D
1
/D
2
/D
3
and E
2
0?
/E
1
0?
//200 mV for DE//50 mV. Figures a,
b and c, correspond to the initial presence of species O
1
,
O
2
and O
3
, respectively.
The behaviour shown in Fig. 1 is in line with Eqs. (9),
(13) /(15). So, when t
2
/t
1
(see curve t
2
/0.025 s in Fig.
1a/c) the DNP technique behaves like the DP techni-
que, whose response is the same whatever the specific
species O
1
, O
2
or O
3
initially present in solution (see Eq.
(13)). In the converse case, when t
2
/t
1
the curves in
DNPV tend to those obtained in dc voltammetry,
according to Eq. (15). In this last technique the response
obtained depends on the species initially present in the
solution [20], with only cathodic current being obtained
when only O
1
is initially present; cathodic and anodic
currents are obtained when only O
2
is present; and only
anodic current when only O
3
is present.
The evolution from the limit case t
2
/t
1
to t
2
/t
1
,
therefore, gives rise to a peculiar physical behaviour of
the normalised DNP curves, depending on the species
initially present, as is shown in these figures. So, except
in the DP case (t
2
/0.025 s), when O
2
is initially present
Scheme 1. Potential /time waveform and points of current measure-
ment for DNP techniques.
M. Lopez-Tenes et al. / Journal of Electroanalytical Chemistry 528 (2002) 159/169 161
the upper and lower limit currents are always different
from zero (Fig. 1b), whereas in Fig. 1a and c the upper
or lower limit current is respectively zero. Identical
curves to those presented in Fig. 1b are obtained when
both species O
1
and O
3
are also initially present in the
solution with identical concentrations (see Eq. (9) with
n
1
/n
2
and g
31
/1).
Fig. 2 shows that the influence of t
2
on the DNP
curves for a DME is qualitatively contrary to that
corresponding to a static electrode, shown in Fig. 1. This
is in accord with the fact that Eq. (9) for the DNP
curves, in the limit t
2
/t
1
, tends to Eq. (15) for a static
electrode and to Eq. (16) in the case of a DME.
In Fig. 3 we have represented the DPV curves
corresponding to a reversible EE process with n
1
/
n
2
/1, D
1
/D
2
/D
3
and DE//40 mV at different
values of E
2
0?
/E
1
0?
. From this figure we deduce that the
height of a peak for an EE mechanism with E
2
0?
/E
1
0?
/
100 mV is considerably lower than that corresponding
to an E simple process with two electrons [9,22] (which is
coincident with the curves of E
2
0?
/E
1
0?
/200 mV in this
figure) with a relative difference in heights of more than
5%. Therefore, both processes can be perfectly distin-
guishable in DPV even when the EE mechanism only
Fig. 1. Inuence of t
2
on the differential normal pulse voltammo-
grams, I
DNPV
/(E
I
/E
1
0?
), for an EE mechanism (Eq. (9) with z/0).
n
1
/n
2
/1, D
1
/D
2
/D
3
, T/298.15 K, E
2
0?
/E
1
0?
//200 mV, DE/
/50 mV, t
1
/0.5 s. The values of t
2
(in s) are on the curves. (a) Only
O
1
is initially present in the solution, (b) only O
2
is initially present in
the solution, (c) only O
3
is initially present in the solution.
Fig. 2. Inuence of t
2
on the differential normal pulse polarograms,
I
DNPV
/(E
I
/E
1
0?
), for an EE mechanism (Eq. (9) with z/2/3). The
values of t
2
(in s) are on the curves. Other conditions as in Fig. 1.
M. Lopez-Tenes et al. / Journal of Electroanalytical Chemistry 528 (2002) 159/169 162
presents one peak (see curves corresponding to 0 and
100 mV). From the above we can conclude that, when
the formal potentials of both steps are very close, DPP
or DPV techniques are more useful than NP or RP
techniques in order to detect a two-step process, since in
the latter, the limit currents remain independent of the
value of E
2
0?
/E
1
0?
and, for example, for E
2
0?
/E
1
0?
/0 the
shape-wave in NP or RP curves is only slightly different
from that corresponding to an E simple process with
two electrons (see Fig. 6 in section below).
Fig. 4 shows the influence of pulse amplitude, DE, on
DPV curves. From this figure it is clear that for a given
value of DE
0?
(/80 mV in this case), a decrease of jDEj
tends to decrease the current of the DPV curves and
tends to separate out into two peaks in agreement with
references [9,22].
When two well-separated peaks are obtained (see
curve of E
2
0?
/E
1
0?
//200 mV in Fig. 3) the first and
second peaks verify J
2
I
, J
2
II
0/ and J
1
I
, J
1
II
0/0, respec-
tively. With the above assumptions in Eq. (13) the
expressions corresponding to the two separate DPV or
DPP curves are:
I
first
DP

(t
1
t
2
)
z
h
z
(b)

t
2
p
n
1
g
31
_
1
1 g
12
J
II
1

1
1 g
12
J
I
1
_
(17)
I
second
DP

(t
1
t
2
)
z
h
z
(b)

t
2
p
n
2
g
31
_
1
1 g
23
J
II
2

1
1 g
23
J
I
2
_
(18)
and the peak parameters [22]
E
I; first peak
E
0?
1

RT
n
1
F
ln g
12

DE
2
I
first peak
DP

(t
1
t
2
)
z
h
z
(b)

t
2
p
n
1
g
32
tanh
_
n
1
FDE
4RT
__
(19)
E
I; second peak
E
0?
2

RT
n
2
F
ln g
23

DE
2
I
I; second peak
DP

(t
1
t
2
)
z
h
z
(b)

t
2
p
n
2
g
31
tanh
_
n
2
FDE
4RT
__
(20)
Note that Eqs. (13) and (17) /(20) are independent of
which species are initially present in the solution but
depend on the sum of the initial concentrations for all
species present.
3.2. Double pulse techniques with potential steps of
variable amplitude: reverse pulse voltammetry (RPV)
and polarography (RPP)
In RP techniques the value of the first applied
potential E
I
is kept constant at a value for which the
surface concentrations of the species initially present in
solution become zero, and the second potential E
II
varies. The RP current I
II
is recorded versus E
II
(see
Scheme 2). Thus, in order to obtain the expressions
corresponding to these techniques, the species initially
present in the solution must be specified as is clearly
indicated in Refs. [23/25]. The same can be said about
the normal pulse (NP) techniques, which are single pulse
techniques whose response can be easily obtained from
the general expressions developed in this paper. To do
that, we must select the first pulse potential E
I
in such a
way that the current I
I
becomes zero, and so it is
imperative to specify the species which are initially
present in solution.
Fig. 3. Inuence of E
2
0?
/E
1
0?
on the differential pulse voltammograms,
I
DPV
/(E
I
/E
1
0?
), for an EE mechanism (Eq. (13) with z/0). DE//40
mV, t
1
/1 s, t
2
/0.03 s. The values of E
2
0?
/E
1
0?
(in mV) are on the
curves. Other conditions as in Fig. 1.
Fig. 4. Inuence of pulse amplitude, DE, on the differential pulse
voltammograms, I
DPV
/(E
I
/E
1
0?
), for an EE mechanism (Eq. (13) with
z/0). E
2
0?
/E
1
0?
//80 mV. The values of DE (in mV) are on the
curves. Other conditions as in Fig. 3.
M. Lopez-Tenes et al. / Journal of Electroanalytical Chemistry 528 (2002) 159/169 163
In the following, we will compare RP and NP
techniques in order to show the analogies and differ-
ences between them in the following initial situations.
3.2.1. Case (a): only species O
1
or O
3
is initially present
When only species O
1
is initially present the RP
current is deduced by making E
I
0// (i.e. J
1
I
0/0 and
J
2
I
0/0) in Eq. (5) whereas to obtain the NP current we
must make E
I
0/ (i.e. J
1
I
0/ and J
2
I
0/) in Eq. (5).
So, we deduce
I
RP
(c
1
)

(2z1)b
_
(n
1
n
2
)g
31
h
z
(b)

_
n
2
g
21
J
II
2
(n
1
n
2
)J
II
1
J
II
2
1 g
23
J
II
2
g
13
J
II
1
J
II
2
_
(21)
I
NP
(c
1
)h
z
(b)
_
(n
1
n
2
)g
31
n
1
g
21
J
II
2
1 g
23
J
II
2
g
13
J
II
1
J
II
2
_
(22)
When only O
3
is initially present, RP and NP
responses must be deduced from Eq. (5) in a contrary
form of the above case, i.e. by making E
I
0/to obtain
I
RP
(c
3

) and E
I
0// to obtain I
NP
(c
3

), so we find
I
RP
(c
3
)

(2z1)b
_
(n
1
n
2
)g
31
h
z
(b)

_
(n
1
n
2
)g
31
n
1
g
21
J
II
2
1 g
23
J
II
2
g
13
J
II
1
J
II
2
_
(23)
I
NP
(c
3
)h
z
(b)
_
n
2
g
21
J
II
2
(n
1
n
2
)J
II
1
J
II
2
1 g
23
J
II
2
g
13
J
II
1
J
II
2
_
(24)
where
I
RP or NP

I
II
FA(t)c

pt
2
D
1

(25)
From Eqs. (21)-(24) it is clear that
I
RP
(c
1
)I
NP
(c
3
)I
NP
(c
1
)I
RP
(c
3
)

(2z1)b
_
(n
1
n
2
)g
31
(26)
Eq. (26) is of great interest since it signifies that the
curves corresponding to RP and NP techniques when
only c
3

is initially present in solution can be easily

obtained from those corresponding to NP and RP
techniques, respectively, when only O
1
is initially pre-
sent.
Moreover, I
RP
(c
1

) and I
NP
(c
1

) verify
I
RP
(c
1
)I
NP
(c
1
)(

(2z1)b
_
h
z
(b))(n
1
n
2
)g
31
(27)
Therefore, we can conclude that it is sufficient to study
only RP or NP curves, according to Eqs. (26) and (27).
It is also interesting to point out that the normalised
I
RPP
(c
1

)/E
II
curves, when only O
1
is initially present
vary with t
2
in such a way that for t
2
/t
1
(b 0/0) (which
is the most usual case) coincide with I
NPP
(c
3

) lower
dashed line in Fig. 5) and with I
dc
(c
1

) upper dashed line

in Fig. 5) when t
2
/t
1
(b 0/1) (note that when t
2
/t
1
the
NPP technique tends to dc polarography). Therefore,
the I
RP
(c
1

) curves vary between I

dc
(c
1

) and I
NP
(c
3

) when
t
2
varies, as is shown in Fig. 5 and Eqs. (26) and (27).
Clearly, if only O
3
is initially present I
RP
(c
3

) curves vary
a converse way.
Fig. 6 shows the influence of E
2
0?
/E
1
0?
on the RP
curves obtained when only O
1
species is initially present.
As can be seen, all these curves have the same limit
current and present a single wave for E
2
0?
/E
1
0?
//100
mV, which separates out into two waves for E
2
0?
/E
1
0?
/
/150 mV. This behaviour is similar to that previously
described in Ref. [20] for the dc curves.
3.2.2. Case (b): only species O
2
is initially present or O
1
,
O
2
and O
3
are initially present with c
1

/c
3

In this case according to the initial conditions we will

suppose that E
2
0?
/E
1
0?
/0 and to obtain the NP response
from Eq. (5) we must substitute E
I
in the same, for an
intermediate potential which fulfils I
I
/0 (see Eq. (1)).
Scheme 2. Potential /time waveform and points of current measure-
ment for RP techniques.
Fig. 5. Inuence of t
2
on the reverse pulse polarograms when only O
1
is initially present, I
RPP
(c
1

)/(E
II
/E
1
0?
), for an EE mechanism (Eq. (21)
with z/2/3). Comparison with I
dc
(c
1

) for t
2
/t
1
and I
NPP
(c
3

) for t
2
/
t
1
. t
1
/1 s. The values of t
2
(in s) are on the curves. Other conditions as
in Fig. 1.
M. Lopez-Tenes et al. / Journal of Electroanalytical Chemistry 528 (2002) 159/169 164
This potential, E(I
I
/0) when n
1
/n
2
/n and D
1
/D
3
for c
1

/c
3

and for any value of c

2

is given by
E(I
I
0)
E
0?
1
E
0?
2
2
(28)
by introducing Eq. (28) in Eq. (5) we deduce
I
NP
(c
1
c
3
; c
2
)nh
z
(b)
_
1 J
II
1
J
II
2
1 g
21
J
II
2
J
II
1
J
II
2
_
(29)
In order to obtain the RP response we can select two
values of E
I
: for E
I
0// conditions of lower limit
current for species c
1

and c
2

, or E
I
0/on conditions of
upper limit current for c
3

and c
2

, by obtaining
[I
RP
(c
1
c
3
; c
2
)]
E
I
0
n
_

(2z1)b
_
h
z
(b)

_
2 g
21
J
II
2
1 g
21
J
II
2
J
II
1
J
II
2
__
(30)
[I
RP
(c
2
; c
1
c
3
)]
E
I
0
n
_

(2z1)b
_
h
z
(b)
_
2J
II
1
J
II
2
g
21
J
II
2
1 g
21
J
II
2
J
II
1
J
II
2
__
(31)
By comparing Eqs. (29) /(31) it is easy to prove that
(I
RP
)
E
I
0
(I
RP
)
E
I
0
2I
NP
(32)
Identical results are found when only species O
2
is
initially present since c
1

/c
3

/0 can be considered as a
particular case of this section.
Fig. 7 shows the two RP curves (Eqs. (30) and (31))
and the NP curve (Eq. (29)) corresponding to this initial
situation. These curves move, depending on the value of
t
2
, between the same limits I
NP
(c
3

) and I
dc
(c
1

), as
explained in the above case.
3.2.3. Case (c): only species O
1
and O
3
are initially
present
In this case it is logical to suppose that E
2
0
?/E
1
0
? /0
and the EE process behaves as a simpler E mechanism.
Thus, to obtain the NP response from Eq. (5), we must
substitute E
I
by
E(I
I
0)
n
1
E
0?
1
n
2
E
0?
2
n
1
n
2

RT
(n
1
n
2
)F
ln
c
1

c
3

(33)
in order to make the current of the first pulse zero.
By introducing Eq. (33) in Eq. (5) we obtain the NP
signal and for deducing the RP curves we must select
E
I
0/ or E
I
0// as in the above case.
3.2.4. Case (d): species O
1
, O
2
and O
3
are initially
present, with c
1

/c
2

/c
3

If we suppose that, in general, the concentrations of

the three species are initially in equilibrium with respect
to the electron exchange reaction in solution, i.e. that
(c
2
)
n
1
n
2
(c
1
)
n
2
(c
3
)
n
1
exp
_
n
1
n
2
F(E
0?
1
E
0?
2
)
RT
_
K (34)
the potential at which I
I
/0 is also given by Eq. (33) and
the NP and RP responses are easily deduced in the same
way as in the above section.
4. Conclusions
We have deduced the equations corresponding to a
double potential step problem for a reversible EE
mechanism.
We have compared the response deduced in differ-
ential pulse methods by analysing the suitability of using
Fig. 6. Inuence of E
2
0?
/E
1
0?
on the reverse pulse voltammograms
when only O
1
is initially present, I
RPV
(c
1

)/(E
II
/E
1
0?
), for an EE
mechanism (Eq. (21) with z/0). t
1
/1 s, t
2
/0.05 s. The values of
E
2
0?
/E
1
0?
(in mV) are on the curves. Other conditions as in Fig. 1.
Fig. 7. Comparison of normal pulse voltammogram, I
NPV
(c
1

/c
3

)/
(E
II
/E
1
0?
) (Eq. (29) with z/0), and reverse pulse voltammograms,
I
RPV
(c
1

/c
3

)/(E
II
/E
1
0?
), (Eq.(30) with z/0) for an EE mechanism
when O
1
, O
2
and O
3
are initially present in the solution with c
1

/c
3

.
E
2
0?
/E
1
0?
//200 mV. Other conditions as in Fig. 6.
M. Lopez-Tenes et al. / Journal of Electroanalytical Chemistry 528 (2002) 159/169 165
DP or DNP, showing that whereas the position of the
DNP response with respect to the zero current line
depends on the species which are initially present in the
solution, the DP curves are not affected, whatever the
species initially present. We have also compared the DP
curves deduced for an EE mechanism with the response
obtained for a simple charge transfer reaction when the
EE response only presents one peak. We have also
pointed out how a decrease in the amplitude of pulse
jDEj tends to decrease the current of the DP curves and
to separate them out into two peaks.
We have also analysed the RP techniques, pointing
out that the species initially present in the solution must
be specified in order to select a suitable RP response.
This is also the case in NP techniques (single pulse),
whose equations can be easily obtained from the general
expressions deduced in this paper. Thus, we have
compared the response obtained in RP and NP techni-
ques.
Acknowledgements
The authors greatly appreciate the nancial support
provided by the Direccio n General Cient ca y Tecnica
(Project No. BQU2000-0231), and by the Fundacio n
Seneca (Project 00696/CV/99). Also M.M.M. thanks
Direccion General Cient ca y Tecnica for a grant
received.
Appendix A
A.1
First pulse
If we consider a planar electrode whose area A(t)
increases with an arbitrary power of time z, i.e. A(t)/
A
0
t
z
[19], when a first potential step E/E
I
is applied
during t with 0/t /t
1
, then the equation system that
describes the mass transport to and from the electrode is
given by

d
I
1
c
I
1
(x; t)

d
I
2
c
I
2
(x; t)

d
I
3
c
I
3
(x; t)0 (A:1)
where

d
I
i

@
@t
D
i
_
@
2
@x
2

zx
t
@
@x
_
i 1; 2; 3 (A:2)
and the boundary value problem is
t0; x0
t0; x 0
_
c
I
1
c
1
; c
I
2
c
2
; c
I
3
c
3
(A:3)
t0; x0
D
1
_
@c
I
1
@x
_
x0
D
2
_
@c
I
2
@x
_
x0
D
3
_
@c
I
3
@x
_
x0
0
(A:4)
c
I
1
(x0)J
I
1
c
I
2
(x0)
c
I
2
(x0)J
I
2
c
I
3
(x0)
(A:5)
with J
1
I
and J
2
I
given by Eq. (3).
This problem has an easy solution, which is given by
Eq. (8) in Ref. [20]. From this reference we can write, for
i /1, 2, 3:
c
I
i
(x; t)c
i
[c
I
i
(x0)c
i
]erfc
_

2z 1
4D
i
t

x
_
(A:6)
being
c
I
1
(x0)
J
I
1
J
I
2
c
1 g
23
J
I
2
g
13
J
I
1
J
I
2
c
I
2
(x0)
J
I
2
c
1 g
23
J
I
2
g
13
J
I
1
J
I
2
c
I
3
(x0)
c
1 g
23
J
I
2
g
13
J
I
1
J
I
2
(A:7)
where
g
mp

D
m
D
p

(A:8)
and c* is given in Eq. (4). The current observed for the
EE mechanism, I
I
, is given by Eq. (1) in this paper [20].
A.2
Second pulse
If at time t
1
the potential is stepped from E
I
to E
II
,
which is applied during t
2
, with 0/t
2
/t
2
and t /t
1
/
t
2
, the equation system to solve is now

d
II
1
c
II
1
(x; t)

d
II
2
c
II
2
(x; t)

d
II
3
c
II
3
(x; t)0 (A:9)
where

d
II
i

@
@t
2
D
i
_
@
2
@x
2

zx
(t
1
t
2
)
@
@x
_
i 1; 2; 3 (A:10)
and the boundary value problem can be now written as
t
2
0; x0
t
2
0; x 0
_
c
II
i
c
I
i
(x; t) i 1; 2; 3 (A:11)
t
2
0; x0
D
1
_
@c
II
1
@x
_
x0
D
2
_
@c
II
2
@x
_
x0
D
3
_
@c
II
3
@x
_
x0
0 (A:12)
M. Lopez-Tenes et al. / Journal of Electroanalytical Chemistry 528 (2002) 159/169 166
c
II
1
(x0)J
II
1
c
II
2
(x0)
c
II
2
(x0)J
II
2
c
II
3
(x0)
(A:13)
with J
1
II
and J
2
II
given by Eq. (7).
Taking into account that the operator

d
II
i
given by Eq.
(A.10) is linear, the solutions corresponding to the
second potential step, c
i
II
(x, t ) can be written as (see
Eq. (A.9))
c
II
i
(x; t)c
I
i
(x; t) c
II
i
(x; t
2
) i 1; 2; 3 (A:14)
where c
i
I
(x, t) are the solutions corresponding to the first
potential step E
I
(see Eq. (A.6)) and c
II
i
(x; t
2
) are the
new unknown partial solutions.
By introducing Eq. (A.14) in Eqs. (A.9), (A.10),
(A.11), (A.12) and (A.13) and taking into account Eqs.
(A.1), (A.2), (A.3), (A.4) and (A.5) for the first pulse, we
deduce that the boundary value problem of this second
pulse is given only in terms of the new unknown
variables c
II
i
(x; t
2
); and has the advantage of having
null initial conditions. In effect, we have

d
II
1
c
II
1
(x; t
2
)

d
II
2
c
II
2
(x; t
2
)

d
II
3
c
II
3
(x; t
2
)0 (A:15)
t
2
0; x0
t
2
0; x 0
t
2
0; x0
_
c
II
i
0 i 1; 2; 3 (A:16)
D
1
_
@ c
II
1
@x
_
x0
D
2
_
@ c
II
2
@x
_
x0
D
3
_
@ c
II
3
@x
_
x0
0 (A:17)
c
II
1
(x0)J
II
1
c
II
2
(x0)(J
II
1
J
I
1
)c
I
2
(x0)
c
II
2
(x0)J
II
2
c
II
3
(x0)(J
II
2
J
I
2
)c
I
3
(x0)
(A:18)
Note that the conditions which must fulfil c
II
1
(x0);
c
II
2
(x0) and c
II
3
(x0) (Eqs. (A.17), (A.18) and (7)),
have a similar form to that corresponding to the first
potential step, E
I
(Eqs. (A.4) and (A.5) and Eq. (3),
respectively), except in the value of the constants
(J
1
II
/J
1
I
)c
2
I
(x/0) and (J
2
II
/J
2
I
)c
3
I
(x/0) in Eq. (A.18),
since the surface concentrations corresponding to the
first potential step, c
1
I
(x/0), c
2
I
(x/0) and c
3
I
(x/0) are
independent of time (see Eq. (A.7)). However, the

d
II
i
operator corresponding to this second pulse is more
complex than that corresponding to the first pulse

d
I
i
(compare Eq. (A.10) and Eq. (A.2), respectively). In
these conditions, in order to solve the differential
equation system (Eq. (A.15)), it is necessary to introduce
in addition the usual variable
s
i

x
2

D
i
t
2
_ i 1; 2; 3 (A:19)
the new dimensionless variable
b
t
2
t
1
t
2
(A:20)
If we also suppose that the functions c
II
i
(x; t
2
) are of the
form:
c
II
i
(x; t
2
)

k0
s
i;k
(s
i
)b
k
i 1; 2; 3 (A:21)
the equation system (Eq. (A.15)) is transformed into:
s
i;k
(s
i
)2s
i
s?
i;k
(s
i
)4ks
i;k
(s
i
)
4zs
i
s?
i;k1
(s
i
)4(k1)s
i;k
(s
i
)
i 1; 2; 3
(A:22)
and Eqs. (A.16), (A.17) and (A.18), corresponding to the
boundary conditions, transform to:
s
i
0 s
i;k
0 i 1; 2; 3 (A:23)
s
i
0

3
i1

D
i
_
s?
i;k
(s
i
0)0 (A:24)
s
1;0
(s
1
0)J
II
1
s
2;0
(s
2
0)(J
II
1
J
I
1
)c
I
2
(x0)
s
2;0
(s
2
0)J
II
2
s
3;0
(s
3
0)(J
II
2
J
I
2
)c
I
3
(x0)
(A:25)
s
1;k
(s
1
0)J
II
1
s
2;k
(s
2
0) k1
s
2;k
(s
2
0)J
II
2
s
3;k
(s
3
0)
(A:26)
By proceeding in the way described in Ref. [26], we
obtain the following expressions for the functions
s
i ,k
(s
i
) (i /1, 2, 3).
k0 s
i;0
(s
i
) c
II
i
(s
i
0)erfc(s
i
) (A:27)
k1 s
i;1
(s
i
)
z

p
p c
II
i
(x0)s
i
e
s
2
i
(A:28)
k2
s
i;2
(s
i
)
z
2

p
p c
II
i
(x0)
_
z 4
6
s
i
zs
3
i
_
e
s
2
i
(A:29)
k3
s
i;3
(s
i
)
z
6

p
p c
II
i
(x0)

_
4 z
2
4
s
i
z(z2)s
3
i
z
2
s
5
i
_
e
s
2
i
(A:30)
k4 s
i;4
(s
i
)
z
24

p
p c
II
i
(x0)

3z
3
56z
2
32z 96
40
s
i

z(5z 8)(z 8)
12
s
3
i

z
2
(5z 8)
2
s
5
i
z
3
s
7
i
_
e
s
2
i
(A:31)
where
c
II
1
(s
i
0)c
_
J
II
1
J
II
2
1 g
23
J
II
2
g
13
J
II
1
J
II
2

J
I
1
J
I
2
1 g
23
J
I
2
g
13
J
I
1
J
I
2
_
c
II
2
(s
i
0)c
_
J
II
2
1 g
23
J
II
2
g
13
J
II
1
J
II
2
M. Lopez-Tenes et al. / Journal of Electroanalytical Chemistry 528 (2002) 159/169 167

J
I
2
1 g
23
J
I
2
g
13
J
I
1
J
I
2
_
c
II
3
(s
i
0)c
_
1
1 g
23
J
II
2
g
13
J
II
1
J
II
2

1
1 g
23
J
I
2
g
13
J
I
1
J
I
2
_
(A:32)
So, taking into account Eq. (A.21), the concentration
profiles given by Eq. (A.14) can be expressed as (i /1, 2,
3):
c
II
i
(x; t)c
I
i
(x; t)

k0
s
i;k
(s
i
)b
k
(A:33)
with the functions s
i ,k
(s
i
) given by Eqs. (A.27), (A.28),
(A.29), (A.30) and (A.31).
The surface concentrations c
i
II
(x/0) corresponding
to an EE mechanism for this second potential step can
be calculated by making x/0 in Eq. (A.33). So, we have
the following (expected) expressions
c
II
1
(x0)
J
II
1
J
II
2
c
1 g
23
J
II
2
g
13
J
II
1
J
II
2
c
II
2
(x0)
J
II
2
c
1 g
23
J
II
2
g
13
J
II
1
J
II
2
c
II
3
(x0)
c
1 g
23
J
II
2
g
13
J
II
1
J
II
2
(A:34)
Note that, as in the case of a reversible E simple process
[27], the surface concentrations of species O
1
, O
2
, and O
3
are independent of time and take the same form for the
first and second potential steps (compare Eq. (A.7) and
Eq. (A.34)). These surface concentrations fulfil the
following relation for any potential step
c
2
(x 0)
n
1
n
2
c
1
(x 0)
n
2
c
3
(x 0)
n
1
exp
_
n
1
n
2
F(E
0?
1
E
0?
2
)
RT
_
K (A:35)
with K being the equilibrium constant corresponding to
the electron exchange reaction (ii).
Once the concentration profiles for this second
potential step E
II
have been obtained (Eq. (A.33)) and
taking into account Eqs. (A.27), (A.28), (A.29), (A.30),
(A.31) and (A.32), the partial currents I
1
II
and I
2
II
are
given by
I
II
1
I
I
1
n
1
FA(t)

D
1
pt
2

h
z
(b)
[c
I
1
(x0)c
II
1
(x0)] (A:36)
I
II
2
I
I
2
n
2
FA(t)

D
1
pt
2

h
z
(b)f
[c
I
1
(x0)c
II
1
(x0)]
g
21
[c
I
2
(x0)c
II
2
(x0)]g (A:37)
where I
1
I
and I
2
I
are the partial currents corresponding to
the application of the first potential pulse E
I
, whose
expressions are [20]
I
I
1
n
1
FA(t)

D
1
(2z 1)
pt

[c
1
c
I
1
(x0)]
I
I
2
n
2
FA(t)

D
1
(2z 1)
pt

f[c
1
c
I
1
(x0)] g
21
[c
2
c
I
2
(x0)]g (A:38)
and
h
z
(b)

(2z 1)b
1 (1 b)
(2z1)

(A:39)
In the particular cases z/0 (static electrode) and z/2/3
(DME), the function h
z
(b) takes the form
h
0
(b)1
h
2=3
(b)

7b
3[1 (1 b)
7=3
]

(A:40)
where h
2/3
(b 0/0) /1; h
2/3
(b 0/1) /7/3. The current
observed, I
II
, corresponding to this second potential step
is deduced by adding Eq. (A.36) and Eq. (A.37) such
that
I
II
I
II
1
I
II
2
(A:41)
so, we deduce
I
II
I
I
FA(t)

D
1
pt
2

h
z
(b)
f(n
1
n
2
)[c
I
1
(x0)c
II
1
(x0)]
n
2
g
21
[c
I
2
(x0)c
II
2
(x0)]g (A:42)
where I
I
is the current corresponding to the first
potential (Eq. (1)). By introducing Eq. (A.7) and Eq.
(A.34) for surface concentrations in Eq. (A.42) we
obtain Eq. (5) of the theory.
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